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Hu P, Lee S, Park KH, et al. Octazethrene and Its Isomer with Different Diradical Characters and Chemical Reactivity: The Role of the Bridge Structure. J Org Chem. 2016;81(7):2911-9doi: 10.1021/acs.joc.6b00172.
Hu, P., Lee, S., Park, K. H., Das, S., Herng, T. S., Gonçalves, T. P., Huang, K. W., Ding, J., Kim, D., & Wu, J. (2016). Octazethrene and Its Isomer with Different Diradical Characters and Chemical Reactivity: The Role of the Bridge Structure. The Journal of organic chemistry, 81(7), 2911-9. https://doi.org/10.1021/acs.joc.6b00172
Hu, Pan, et al. "Octazethrene and Its Isomer with Different Diradical Characters and Chemical Reactivity: The Role of the Bridge Structure." The Journal of organic chemistry vol. 81,7 (2016): 2911-9. doi: https://doi.org/10.1021/acs.joc.6b00172
Hu P, Lee S, Park KH, Das S, Herng TS, Gonçalves TP, Huang KW, Ding J, Kim D, Wu J. Octazethrene and Its Isomer with Different Diradical Characters and Chemical Reactivity: The Role of the Bridge Structure. J Org Chem. 2016 Apr 01;81(7):2911-9. doi: 10.1021/acs.joc.6b00172. Epub 2016 Mar 21. PMID: 26966788.
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J Org Chem. 2016 Apr 01;81(7):2911-9. doi: 10.1021/acs.joc.6b00172. Epub 2016 Mar 21.

Octazethrene and Its Isomer with Different Diradical Characters and Chemical Reactivity: The Role of the Bridge Structure.

The Journal of organic chemistry

Pan Hu, Sangsu Lee, Kyu Hyung Park, Soumyajit Das, Tun Seng Herng, Théo P Gonçalves, Kuo-Wei Huang, Jun Ding, Dongho Kim, Jishan Wu

Affiliations

  1. Department of Chemistry, National University of Singapore , 3 Science Drive 3, 117543 Singapore.
  2. Spectroscopy Laboratory for Functional ?-Electronic Systems and Department of Chemistry, Yonsei University , Seoul 120-749, Korea.
  3. Department of Materials Science & Engineering, National University of Singapore , 119260 Singapore.
  4. Division of Physical Science and Engineering and KAUST Catalysis Center, King Abdullah University of Science and Technology (KAUST) , Thuwal 23955-6900, Kingdom of Saudi Arabia.

PMID: 26966788 DOI: 10.1021/acs.joc.6b00172

Abstract

The fundamental relationship between structure and diradical character is important for the development of open-shell diradicaloid-based materials. In this work, we synthesized two structural isomers bearing a 2,6-naphthoquinodimethane or a 1,5-naphthoquinodimethane bridge and demonstrated that their diradical characters and chemical reactivity are quite different. The mesityl-or pentafluorophenyl-substituted octazethrene derivatives OZ-M/OZ-F and their isomer OZI-M (with mesityl substituents) were synthesized via an intramolecular Friedel-Crafts alkylation followed by oxidative dehydrogenation strategy from the key building blocks 4 and 11. Our detailed experimental and theoretical studies showed that both isomers have an open-shell singlet ground state with a remarkable diradical character (y0 = 0.35 and 0.34 for OZ-M and OZ-F, and y0 = 0.58 for OZI-M). Compounds OZ-M and OZ-F have good stability in an ambient environment, while OZI-M has high reactivity and can be easily oxidized to a dioxo product 15, which can be correlated to their different diradical characters. Additionally, we investigated the physical properties of OZ-M, OZ-F, and 15.

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